CN1155687C - Bleaching compositions - Google Patents

Abstract

Granular detergent compositions and in particular low density, phosphate containing detergent compositions comprise a specific bleaching system containing hydrophobic peracid bleach and hydrophilic peracid bleach and a peroxide source. These detergent compositions have specific low levels of available oxygen from hydrophobic aid hydrophilic peroxyacid bleach, specific ratios of available oxygen from the hydrophobic peracid bleach to the hydrophilic peracid bleach and specific ratios of available oxygen of the peroxide source to the available oxygen of the peracids. These specific mixed bleach systems are useful for sanitization or reduction of bacterial activity.

Description

bleaching composition

field of invention

The present invention relates to bleach-containing compositions suitable for use in laundry methods.

Background of the invention

During the past few decades, research efforts have been directed towards the development of organic peroxyacid based bleaching systems that are effective in removing stains and/or soils from fabrics at lower wash temperatures. Organic peroxyacids are generally obtained by in situ perhydrolysis of organic peroxyacid bleach precursor compounds (bleach activators).

A commonly used precursor compound is tetraacetylethylenediamine (TAED), which has effective hydrophilic cleaning power, especially on beverage stains. In order for a detergent to achieve effective bleaching power, both hydrophobic and hydrophilic stains need to be bleached by the bleaching system. Organic peroxyacid precursors have therefore additionally been developed to treat hydrophobic stains and soils. There are various documents disclosing the use of mixtures of hydrophobic and hydrophilic bleaching agents in detergents, eg JP 7-238298, DE 196,16,782, WO 94/28103.

However, the inventors have found that most of the prior art bleaching compositions when used under adverse conditions, such as low temperature washing, washing with limited agitation, use of low levels of detergent actives, highly soiled fabrics, presence of high Content of metal ions or after storage at high humidity or high temperature does not always function satisfactorily. These problems occur especially in low density detergents, especially when the total amount of bleaching system in the detergent composition is low, and these problems also occur in detergents containing high levels of phosphate builders, such washing Agents can introduce metal ions into the wash.

Additionally, in order to have an effective bleaching system, the bleaching system should provide excellent bleaching power at low levels, thereby reducing the likelihood of fabric damage.

Therefore, there is a need to provide detergent compositions comprising low levels of bleach systems which have very effective bleaching performance on both hydrophobic and hydrophilic soils under adverse conditions.

The present inventors have now surprisingly found that improved bleaching power under adverse conditions can be obtained by using bleaching compositions containing low amounts of bleach activators and peroxide sources, i.e. said bleaching compositions have bleach activation from hydrophobic to hydrophilic The effective oxygen (AvO) obtained by the agent is lower than 5000ppm and has a specific ratio of hydrophobic activator AvO to hydrophilic activator AvO, that is, 3:1-1:50, and has a specific ratio of total AvO to activator AvO, that is, greater than 2:1. The bleaching system has been found to be particularly suitable for use in low density detergents, hand wash detergents, phosphate-containing compositions and also in washing processes using low concentrations of detergent.

In general, bleach, especially hypochlorite bleach, is known to kill bacteria. High levels of bleach are often required to sufficiently reduce or eliminate bacteria. Consequently, most detergents comprising bleach systems known in the art, which contain only low levels of bleach, are not effective as disinfecting biocides.

The present inventors have found that mixed bleach systems comprising specific levels and ratios of hydrophobic, hydrophilic bleach additives and peroxide sources are very useful as biocides.

They have found that even low levels of specific bleaching compositions used in wash solutions or detergents or cleansers can provide effective disinfection to laundered fabrics or surfaces, or when the bleaching components are used in the specific proportions mentioned above, can effectively Reduce bacteria.

All documents cited in this specification are hereby incorporated by reference in relevant part.

Summary of the invention

The present invention relates to detergent compositions having a density of 330 g/l to 700 g/l comprising a bleaching system comprising a hydrophilic and hydrophobic peracid bleach or peracid bleach precursor and a peroxide source, characterized in that The total amount of available oxygen (AvO-a) obtained from hydrophilic and hydrophobic peracid bleaches or bleach precursors is less than 5000 ppm, and the available oxygen (AvO-hb) of hydrophobic peracids or precursors is combined with hydrophilic peracids or The ratio of available oxygen (AvO-hp) of the precursor is 3:1-1:50, and the ratio of available oxygen (AvO-o) to AvO-a of the peroxide source is at least 2:1.

Detailed description of the invention

In the detergent compositions of the present invention, the total amount of available oxygen (AvO-a) obtained from hydrophilic and hydrophobic peracid bleaches or bleach precursors is less than 5000 ppm, or even less than 4000 ppm, or even less than 3000 ppm , or even below 2500ppm.

The ratio of the available oxygen (AvO-hb) of the hydrophobic peracid or precursor to the available oxygen (AvO-hp) of the hydrophilic peracid or precursor is 3:1-1:50, more preferably 2.5:1-1:30 , or even 2:1-1:20.

The peroxide source has a ratio of available oxygen (AvO-o) to AvO-a of at least 2:1, preferably at least 3:1, or even 4:1.

The composition preferably has a density of 370-700 g/l, or even to 650 g/l, or even to 600 g/l.

Preferably the composition is a low density granular composition, especially a phosphate containing composition, especially a high sudsing composition, a soaking or pretreatment composition, a handwashing composition.

Accordingly, the present invention also relates to a method of washing clothes by hand or pretreating or soaking clothes, wherein a detergent composition according to the invention is used.

The present invention also relates to the reduction of bacterial activity using a bleaching composition comprising hydrophobic and hydrophilic peracid bleaches or precursors thereof and a source of peroxide wherein the ratio of AvO-hb to AvO-hp is 3:1 - 1:50, preferably 2.5:1-1:10, even 2:1-1:20, and wherein the ratio of AvO-o to AvO-a is at least 2:1, preferably at least 3:1, or even 4: 1.

"Reducing the activity of a bacterium" as used herein includes killing the bacterium or part of the bacterium and inhibiting further growth or development of the bacterium.

Preferably the bleaching composition is used to disinfect fabrics or surfaces cleaned with the bleaching composition. Preferably then, the sanitizing method comprises contacting with the composition a fabric or surface containing bacteria, in particular bacteria present in stains on the fabric or surface. Accordingly, the present invention also includes a method of disinfecting fabrics, wherein fabrics are contacted with a composition or a solution of a composition comprising hydrophilic and hydrophobic peracid bleaches or precursors thereof and a source of peroxide, characterized in that the hydrophobic The ratio of the available oxygen (AvO-hb) of the peracid or precursor to the available oxygen (AvO-hp) of the hydrophilic peracid or precursor is 3:1-1:50, and the available oxygen of the peroxide source (AvO- o) a ratio of at least 2:1 to the total amount of available oxygen (AvO-a) derived from hydrophilic and hydrophobic peracid bleaches.

The bleaching composition is preferably present in a cleaning composition for cleaning fabrics or surfaces, preferably a laundry or dishwashing detergent or a hard surface cleaner. Preferred are laundry detergent compositions comprising the components described herein.

The amount of AvO-a in cleaning or detergent compositions or solutions thereof which preferably contain a bleaching composition and are used to reduce bacterial activity is preferably up to 10000 ppm, more preferably up to 5000 ppm, or even 4000 ppm, or even 3000 ppm or 2500 ppm.

Preferred hydrophilic and hydrophobic peracid bleaches or precursors thereof and preferred sources of peroxide are described below.

Hydrophobic and hydrophilic peracids or peracid precursors

An essential feature of the detergent compositions of the present invention are hydrophobic peracids or precursors thereof.

The bleaching system preferably comprises a hydrophobic percarboxylic acid and/or precursor thereof of the formula:

R ¹ -CO ₃ M

wherein ^R has at least 6 carbon atoms and M is a counterion; or the formula:

R ¹ -CO-L

wherein L is a leaving group attached to a ^R1 -CO-group having an oxygen atom, and ^R1 has at least 6 carbon atoms. Preferred leaving groups are benzoic acid and its derivatives, especially besylate.

Percarboxylic acid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to form percarboxylic acids.

The counter ion M of the percarboxylic acid is preferably sodium, potassium or hydrogen.

Preferably the parent carboxylic acid of such a hydrophobic peracid or precursor thereof has a critical micelle concentration of less than 0.5 mol/liter and wherein said critical micelle concentration is determined in aqueous solution at 20°C to 50°C.

Percarboxylic acids, preferably formed from precursors, preferably contain at least 7 carbon atoms, or at least 8 or even 9 carbon atoms, preferably they contain 7-12 carbon atoms, more preferably 8-11 carbon atoms , most preferably 9 or 10 carbon atoms. In a preferred aspect, the percarboxylic acid or peroxyacid formed from the precursor has an alkyl chain of at least 7 carbon atoms, more preferably at least 8 carbon atoms, most preferably 9 carbon atoms.

The percarboxylic acid precursor can be any of the esters described for use in laundry detergents as bleach activators, such as the alkyl percarboxylic acid precursors described herein, sugar esters such as pentaacetylglucose, imidate esters such as benzene Ethyl imidate, triacyl cyanurate such as triacetyl cyanurate and tribenzoyl cyanurate, the ester can produce relatively surface active oxidation products such as described in GB-A-864798, GB-A-864798 - a C _8-18 alkanoic or aralkanoic acid in A-1147871, the esters being described in EP-A-98129 and EP-A-106634.

Preference may be given to phenyl esters of _C14-22 alkanoic or alkenoic acids, esters of hydroxylamines, lower alkanoic acids and bis-diesters of diols, such as those described in EP-A-0125781, especially 1 , 1,5-triacetoxypent-4-ene and 1,1,5,5-tetraacetoxypentane and the corresponding butene and butane compounds, for example in EP-A-0140648 and EP-A-0092932 Ethylene benzoate acetate and di(ethylene acetate) adipate and enol esters described in .

Other highly preferred hydrophobic alkyl percarboxylic acid precursors include decanoyloxybenzoic acid or salts thereof, sodium or potassium dodecanoyloxybenzenesulfonate, sodium or potassium decanoyloxybenzenesulfonate (DOBS ), sodium or potassium benzoyloxybenzenesulfonate (BOBS), more preferably sodium or potassium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS) and even more preferably nonanoyl Sodium or Potassium Oxybenzene Sulfonate (NOBS).

Amide substituted bleach activator compounds such as those described in EP-A-0170386 are also useful herein. Suitable examples of such reagents include precursors or acids such as (6-hexylamino)-6-oxo-hexanoic acid, (6-octylamino)-6-oxo-hexanoic acid, (6-nonylamino )-6-oxo-caproic acid, (6-decylamino)-6-oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate, m-chloroperbenzoate, 4-nonyl Amino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid, or precursors thereof, especially precursors having a benzenesulfonate leaving group. Such bleaching agents are disclosed in US Patents US4483781, US4634551, EP0133354, US4412934 and EP0170386.

Other suitable organic peroxyacids include diperoxyalkanedioic acids having more than 7 carbon atoms, such as diperoxydodecanedioic acid (DPDA), diperoxytetradecanedioic acid, and diperoxyhexadecanedioic acid Alkanedioic acid. Mono- and diperazelaic acid, mono- and diperbrazil acid, and N-phthaloylaminoperoxycaproic acid (PAP), nonanoylamidoperoxyadipate (NAPAA) and hexanesulfinylperoxy Propionic acid is also suitable for the present invention.

The composition also comprises a hydrophilic peracid or precursor thereof, preferably having the formula:

R ¹ -CO ₃ M

wherein ^R has less than 6 carbon atoms and M is a counterion; or the formula:

R ¹ -CO-L

wherein L is a leaving group attached to a ^R1 -CO- group having an oxygen atom, and ^R1 has less than 6 carbon atoms.

A preferred hydrophilic precursor is TAED.

source of peroxide

Inorganic perhydrate salts are a preferred source of peroxide. Preferably these salts are present in an amount of 0.01% to 30% by weight, more preferably 0.5% to 10%.

Examples of inorganic perhydrate salts include: perborates, percarbonates, perphosphates, persulfates and persilicates. Inorganic perhydrate salts are generally alkali metal salts. Inorganic perhydrate salts may be incorporated as crystalline solids without additional protection. However, for certain perhydrate salts, the preferred aspect of the granular composition is to use a coated form of the material to provide the perhydrate salt with good storage stability in the granular product. Suitable coating materials include inorganic salts such as alkali metal silicates, carbonates or borates, or mixtures thereof, or organic substances such as waxes, oils or fatty soaps.

Sodium perborate is the preferred perhydrate salt, _which can be in _{the form of} the monohydrate or the _{tetrahydrate NaBO2H2O2-3H2O} of the nominal formula _NaBO2H2O2 .

Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates of the present invention. Sodium percarbonate is _an addition compound having _the formula corresponding to _{2Na2CO3-3H2O2} , which is commercially available as a _crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt useful in the detergent compositions herein.

other detergent ingredients

The detergent compositions of the present invention may also contain other detergent ingredients. The exact nature of these additional components and the amount incorporated therein will depend upon the physical form of the composition or component and the exact nature of the laundering operation in which it is used.

The compositions of the present invention preferably comprise one or more other detergent ingredients selected from other surfactants, other bleaches, bleach catalysts, alkaline systems, builders, phosphate-containing builders, organic polymeric substances, enzymes, foam suppressors, calcium soap dispersants, soil suspending and anti-redeposition agents, soil release agents, fragrances, brighteners, photobleaches and other corrosion inhibitors.

bleach catalyst

The bleach system may contain a transition metal-containing bleach catalyst.

A suitable type of bleach catalyst is one comprising transition metal cations such as copper, iron or manganese cations having defined bleach catalytic activity, auxiliary metal cations such as zinc or aluminum cations having little or no bleach catalytic activity, and catalytic and Catalyst systems assisting chelating agents with stability constants defined by metal cations, in particular ethylenediaminetetraacetic acid, ethylenediaminetetrakis(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in US 4,430,243.

Other types of bleach catalysts include the manganese-based complexes disclosed in US 5,246,621 and US 5,244,594. Preferable examples of these catalysts include: Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO ) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4 , 7-triazacyclononane) ₄ (ClO ₄ ) ₂ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-tri Azacyclononane) ₂ (ClO ₄ ) ₃ , and mixtures thereof. Others are described in European Patent Application Publication No. 549272. Other ligands suitable for use in the present invention include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane alkanes, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

Examples of suitable bleach catalysts are found in US 4,246,612 and 5,227,084. See also US 5,194,416 which teaches mononuclear manganese(IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH ₃ ) ₃ (PF ₆ ).

Another class of bleach catalysts as disclosed in US 5114606 are water-soluble complexes of manganese (III) and/or (IV) with non-carboxylate polyol ligands having at least three consecutive C-OH groups thing. Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adolitol, meso-erythritol, meso-inositol, Lactose and its mixtures.

US Patent No. 5,114,611 teaches bleach catalysts comprising complexes of transition metals including Mn, Co, Fe or Cu with non-(macro)cyclic ligands. The ligand has the formula:

wherein each of R ¹ , R ² , R ³ and R ⁴ can be selected from H, substituted alkyl and aryl such that each of R ¹ -N=CR ² and R ³ -C=NR ⁴ forms a five- or six-membered ring . The rings can also be substituted. B is a bridging group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C═O, wherein each of R ⁵ , R ⁶ and R ⁷ can be H, alkyl or aryl, including substituted or unsubstituted groups group. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, the rings may be substituted with substituents such as alkyl, aryl, alkoxy, halogen and nitro. Particular preference is given to the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe-bispyridylmethane and bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine) _Cl2 , bis(isothiocyanato)bispyridylamine cobalt(II), tripyridylamine cobalt(II) perchlorate, Co( 2,2-bispyridylamine) ₂ O ₂ ClO ₄ , bis(2,2'-bispyridylamine)copper(II) perchlorate, tris(bis-2-pyridylamine)iron(II) perchlorate Salt and mixtures thereof. Highly preferred may be manganese bridged cyclams such as Mn dichlorocyclam or Mn 1,4,8,11-tetraazacyclotetradecane.

Other examples include dinuclear Mn complexes with tetra-N-dentate and di-N-dentate ligands, including N ₄ Mn ^III (uO) ₂ Mn ^IV N ₄ ⁺ ) and [(2,2 '-bipyridine) ₂ Mn ^III (uO) ₂ Mn ^IV (2,2'-bipyridine) ₂ ]-(ClO ₄ ) ₃ .

Other bleach catalysts are disclosed in, for example, European Patent Application Publication No. 408,131 (cobalt complex catalysts), European Patent Application Publication Nos. 384,503 and 306,089 (metal-porphyrin catalysts), US 4,728,455 (manganese/polydentate ligand catalysts), US 4,711,748 and European Patent Application Publication No. 224,952 (manganese catalysts adsorbed on aluminosilicates), US 4,601,845 (manganese and zinc or magnesium salts supported on aluminosilicates), US 4,626,373 (manganese /ligand catalyst), US 4,119,557 (iron complex catalyst), DE 2,054,019 (cobalt chelate catalyst), CA 866,191 (transition metal-containing salt), US 4,430,243 (chelating agent with manganese cation and non-catalytic metal cation ) and US 4,728,455 (manganese gluconate catalyst). Highly preferred may be pentamamine cobalt(III) dichloride acetate.

Bleach catalysts are generally used in the compositions and methods of the present invention in catalytically effective amounts. By "catalytically effective amount" is meant an amount sufficient to enhance the bleaching and removal of the stain or some stain of concern on the target substrate, whatever the comparative test conditions used. The test conditions will vary according to the type of washing equipment used and the habits of the user. Some users choose to use very hot water; others use warm or even cold water in their washing operations. Of course, the catalytic performance of the bleach catalyst will be influenced by these considerations and the amount of bleach catalyst employed in fully formulated detergent and bleach compositions can be appropriately adjusted. Indeed, without limitation, the compositions and methods of the present invention can be adjusted to provide at least about one part per million active bleach catalyst in the wash solution, preferably about 0.2 ppm to about 200 ppm catalyst in the wash solution, preferably 0.4-100ppm catalyst. To further illustrate this point, about 3 micromolar manganese catalyst was effective under European conditions at 40°C, pH 10 using perborate and bleach precursors. Under US conditions, a 3-5 fold increase in concentration may be required to obtain the same results.

Surfactant

The detergent compositions of the present invention preferably contain one or more surfactants selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, ampholytic surfactants, amphoteric surfactants Amphoteric, zwitterionic surfactants and mixtures thereof.

A general list of anionic, nonionic, amphoteric and zwitterionic surfactant classes and classes of such surfactants is given in US Patent 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Additional examples are given in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in US 4,259,217, issued March 31, 1981 to Murphy.

Ampholytic, amphoteric and zwitterionic surfactants, when present, are generally used in combination with one or more anionic and/or nonionic surfactants.

anionic surfactant

The detergent compositions according to the invention preferably comprise additional anionic surfactants. Essentially any anionic surfactant useful for detersive purposes can be included in the present detergent compositions. These may include anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts). Anionic sulfate and sulfonate surfactants are preferred.

Highly preferred surfactant systems comprise sulfonate and sulfate surfactants as described herein, preferably linear or branched chain alkylbenzene sulfonates and alkyl ethoxy sulfates, preferably in combination as described herein of cationic surfactants.

Other anionic surfactants include isethionates such as acyl isethionates, N-acetyl taurates, fatty acid amides of methyl taurine, alkyl succinates, and alkyl sulfosuccinates salts, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₄ diesters) , N-acyl sarcosinate. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow.

Anionic Sulfate Surfactant

Anionic sulfate surfactants suitable for use herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenol oxirane ether sulfates , C ₅ -C ₁₇ acyl-N-(C ₁ -C ₄ alkyl) and -N-(C ₁ -C ₂ hydroxyalkyl) glucosamine sulfates, and sulfates of alkyl polysaccharides such as alkyl Sulfate salts of polyglucosides (non-ionic non-sulfated compounds are described below).

Alkyl sulfate surfactants are preferably selected from linear and branched primary C ₁₀ -C ₁₈ alkyl sulfates, more preferably C ₁₁ -C ₁₅ branched chain alkyl sulfates and C ₁₂ -C ₁₄ linear alkyl sulfates Salt.

The alkyl ethoxy sulfate surfactants are preferably selected from C ₁₀ -C ₁₈ alkyl sulfates ethoxylated with 0.5 to 20 moles of ethylene oxide per mole. More preferably, the alkyl ethoxy sulfate surfactant is a C ₁₁ -C ₁₈ , most preferably a C ₁₁ -C ₁₅ alkane ethoxylated with 0.5-7, preferably 1-5 moles per mole of ethylene oxide. base sulfate.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/or sulfonate and alkyl ethoxy sulfate surfactants. Such mixtures are described in PCT Patent Application No. WO 93/18124.

Anionic Sulfonate Surfactant

Anionic sulfonate surfactants suitable for use in the present invention include C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ - _C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfonates, and any mixtures thereof.

Anionic Carboxylate Surfactants

Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxy" soaps), especially as described herein. Certain secondary soaps.

Suitable alkyl ethoxy carboxylates include those having the formula RO(CH ₂ CH ₂ O) _x CH ₂ COO ^- M ⁺ , wherein R is C ₆ -C ₁₈ alkyl, x is 0-10, E The oxide distribution should be such that the amount of species where x is 0 is less than 20% by weight and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-( _CHR1 - _CHR2 -O) _-R3 wherein R is a _C6 - _C18 alkyl group and x is 1 -25, R ₁ and R ₂ are selected from hydrogen, methyl acid groups, succinic acid groups, hydroxysuccinic acid groups and mixtures thereof, R ₃ is selected from hydrogen, substituted or unsubstituted with 1-8 carbon atoms hydrocarbons, and mixtures thereof.

Suitable soap surfactants include secondary soap surfactants comprising carboxyl units attached to secondary carbon atoms. Preferred secondary soap surfactants for use in the present invention are water-soluble materials selected from the group consisting of water-soluble salts of 2-methyl-1-undecanoic acid, water-soluble salts of 2-ethyl-1-decanoic acid , the water-soluble salts of 2-propyl-1-nonanoic acid, the water-soluble salts of 2-butyl-1-octanoic acid and the water-soluble salts of 2-pentyl-1-heptanoic acid.

Certain soaps can also be added as suds suppressors.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CON(R ¹ )CH ₂ COOM, wherein R is C ₅ -C ₁₇ linear or branched chain alkyl or alkenyl, and R ¹ is C ₁ -C ₄ alkyl, M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the sodium salt form.

Alkoxylated Nonionic Surfactants

Essentially any alkoxylated nonionic surfactant is suitable for use in the present invention. Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants may be selected from nonionic alkylphenol condensates, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylated/propoxylated condensates with propylene glycol, and nonionic ethoxylated condensation products with propylene oxide/ethylenediamine adducts.

Nonionic Alkoxylated Alcohol Surfactants

Condensation products of fatty alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and/or propylene oxide, are suitable for use in the present invention. The alkyl chain of the fatty alcohol may be straight or branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Particular preference is given to condensation products of alcohols having alkyl groups of 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use in the present invention are those having the formula: R ² CONR ¹ Z, where R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy , propoxy or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (ie methyl); R ² is C ₅ -C ₃₁ hydrocarbon, preferably Straight chain C ₅ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₇ alkyl or alkenyl, or a mixture thereof; Z is a polyhydroxyhydrocarbyl group having a linear hydrocarbyl chain directly attached to at least 3 hydroxyl groups, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those of the formula: R ⁶ CON(R ⁷ ) ₂ , wherein R ⁶ is an alkyl group comprising 7-21, preferably 9-17 carbon atoms, each R ⁷ being selected from hydrogen , C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and -(C ₂ H ₄ O) _x H, wherein x is 1-3.

Nonionic Alkyl Polysaccharide Surfactant

Alkyl polysaccharides suitable for use in the present invention are described in US 4,565,647, Llenado, issued January 21, 1986, they have hydrophobic groups containing 6-30 carbon atoms, and polysaccharides containing 1.3-10 sugar units are hydrophilic groups, such as polyglycosides.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x

Wherein ^R is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl contains 10-18 carbon atoms; n is 2 or 3; t is 0-10; x 1.3-8. The glycosyl is preferably derived from glucose.

amphoteric surfactant

Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds of the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ wherein R ³ is selected from the group consisting of alkyl, hydroxyalkyl, acylamidopropyl and Alkylphenyl, or a mixture thereof; R ⁴ is an alkylene or hydroxyalkylene group containing 2-3 carbon atoms, or a mixture thereof; x is 0-5, preferably 0-3; each R ⁵ is a Alkyl or hydroxyalkyl groups of 1-3 carbon atoms, or polyethylene oxide groups containing 1-3 oxirane groups. Preference is given to C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₁₀ -C ₁₈ acylamidoalkyldimethylamine oxides.

An example of a suitable alkylamphodicarboxylic acid is Miranol (TM) C2M Conc., manufactured by Miranol, Inc., Dayton, NJ.

zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent compositions herein. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are examples of zwitterionic surfactants useful in the present invention.

Suitable betaines are those compounds having the formula: R(R') ₂ N ⁺ R ² COO ^- , wherein R is C ₆ -C ₁₈ hydrocarbyl, each R ¹ is typically C ₁ -C ₃ alkyl, R ² is a C ₁ -C ₅ hydrocarbon group. Preferred betaines are C ₁₂ -C ₁₈ dimethylammonium hexanoate and C ₁₀ -C ₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaine. Complex betaine surfactants are also suitable for use in the present invention.

cationic surfactant

Suitable cationic surfactants for use in the detergents of the present invention include quaternary ammonium surfactants. Quaternary ammonium surfactants are preferably mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants in which the remaining positions of N are substituted by methyl, hydroxyethyl or hydroxypropyl groups . Also preferred are monoalkoxylated and bisalkoxylated amine surfactants.

Another group of suitable cationic surfactants which may be used in the detergent compositions or components thereof of the present invention are cationic ester surfactants. Such cationic ester surfactants are preferably water-dispersible, compounds having surfactant properties comprising at least one ester linkage (ie -COO-) and at least one cationic charged group.

Suitable cationic ester surfactants include choline ester surfactants such as those disclosed in US 4,228,042, 4,239,660 and 4,260,529.

In a preferred case, the ester bond and the cationic charged group are separated from each other in the surfactant molecule by a spacer consisting of a chain comprising at least three atoms (i.e. three atoms chain length), preferably 3-8 atoms, more preferably 3-5 atoms, most preferably 3 atoms. The atoms forming the spacer chain are selected from carbon, nitrogen and oxygen atoms and any mixtures thereof, provided that any nitrogen or oxygen atom in said chain is bonded only to a carbon atom in the chain. Thus, spacers having linkages such as -OO- (ie peroxide), -NN- and -NO- are excluded and spacers having linkages such as _-CH2 -O- _CH2- and _-CH2 -NH- _CH2 - a spacer for the bond. In preferred cases, the spacer chain comprises only carbon atoms, most preferably said chain is a hydrocarbyl chain.

Cationic Monoalkoxylated Amine Surfactants

Highly preferred herein are cationic monoalkoxylated amine surfactants having the general formula I:

wherein ^R is an alkyl or alkenyl moiety containing from about 6 to 18 carbon atoms, preferably from 6 to about 16 carbon atoms, most preferably from about 6 to 14 carbon atoms; R ^{and R} are each independently 1-Alkyl of about 3 carbon atoms, preferably methyl, most preferably ^R2 and ^R3 are both methyl; ^R4 is selected from hydrogen (preferred), methyl and ethyl, X ^- is to provide electrical neutrality Anions such as chlorine, bromine, methylsulfate, sulfate, etc. A is alkoxy, especially ethoxy, propoxy or butoxy; p is 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.

Preferably ^ApR4 is a hydroxyalkyl group having no more than 6 carbon atoms, whereby the -OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly _{preferred ApR4 groups are -CH2CH2OH, -CH2CH2CH2OH, -CH2CH} ⁽ _{CH3 ) OH and -CH ( CH3 ) CH2OH} , _-CH2CH2OH is particularly preferred. Preferably the ^R1 group is a straight chain alkyl group. Straight chain ^R groups having 8-14 carbon atoms are preferred.

Another highly preferred cationic monoalkoxylated amine surfactant for use herein has the formula:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ -C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl, and X is any suitable anion providing charge balance, preferably chlorine or bromine.

As noted, compounds of the above type include those in which ethoxy (CH ₂ CH ₂ O) units (EO) are replaced by butoxy, isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH( Those replaced by CH ₃ O] units (i-Pr) or n-propoxy units (Pr) or mixtures of EO and/or Pr and/or i-Pr units.

The level of cationic monoalkoxylated amine surfactants used in the detergent compositions of the present invention is preferably from 0.1% to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% by weight of the composition -3.0%.

Cationic dialkoxylated amine surfactants

Cationic dialkoxylated amine surfactants preferably have the general formula II:

wherein R ¹ is an alkyl or alkenyl moiety containing about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably about 10 to about 14 carbon atoms; R ² is an alkyl or alkenyl moiety containing 1 to 3 Alkyl of carbon atoms, preferably methyl; ^R3 and ^R4 can vary independently, they are selected from hydrogen (preferred), methyl and ethyl; X ^- is an anion sufficient to provide electrical neutrality, such as chlorine, bromine , Methylsulfate, Sulfate, etc. A and A' can vary independently, each selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie -CH ₂ CH ₂ O), propoxy, butoxy and mixtures thereof; p is 1 to about 30, preferably 1 to about 4, q is 1 to about 30, preferably 1 to about 4, most preferably both p and q are 1.

Highly preferred cationic dialkoxylated amine surfactants for use herein have the formula:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof, and X is any suitable anion providing charge balance, preferably chlorine. With regard to the general structure of the above cationic dialkoxylated amines, in preferred compounds ^R1 is derived from (coco) _C12 - _C14 alkyl moiety fatty acid, ^R2 is methyl, ^ApR3 and A'qR ⁴ are all monoethoxy groups.

Other cationic dialkoxylated amine surfactants suitable for use herein include compounds of the formula:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₄ alkyl, p is independently 1 to about 3, q is 1 to about 3, R ² is C ₁ -C ₃ alkyl, preferably methyl , X is an anion, especially chlorine or bromine.

Other compounds of the above type include those in which ethoxy (CH ₂ CH ₂ O) units (EO) are replaced by butoxy (Bu), isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH(CH ₃ O] units (i-Pr) or n-propoxy units (Pr) or mixtures of EO and/or Pr and/or i-Pr units instead.

water soluble builder compound

The detergent compositions herein preferably comprise water-soluble builder compounds, typically at a level of 1-80%, preferably 10-60%, more preferably 15-40%, by weight of the composition.

The detergent compositions of the present invention preferably comprise phosphate-containing builder materials. Based on the weight of the composition, the content is preferably 0.5%-60%, more preferably 5%-50%, more preferably 8%-40%.

Phosphate-containing builder materials preferably comprise tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or co-polymeric polycarboxylates or salts thereof, wherein the polycarboxylic acids are separated from each other by not more than two carbon atoms The builder compound also includes borate salts and mixtures of any of the foregoing.

Carboxylate or polycarboxylate builders can be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylate salts containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, glyoxylic acid, tartaric acid, tartronic acid, and fumaric acid , and ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxy groups or their acids including, inter alia, the water-soluble citrates, aconitates and citraconates, and succinate derivatives such as carboxymethoxysuccinate as described in British Patent 1,379,241 salts, lactyloxysuccinates described in British Patent 1389732, aminosuccinates described in Dutch Patent 7205873, and oxygen polycarboxylate substances such as 2-oxa-1 , 1,3-propane tricarboxylate. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8%, by weight of the composition.

Polycarboxylates containing four carboxyl groups include oxydisuccinates described in British Patent 1,261,829, and 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates salt and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patents 1,398,421 and 1,398,422 and US Patent No. 3,936,448, and the sulfonated pyrolyzed citrates described in British Patent 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, more particularly citrates.

Mixtures of monomeric or oligomeric polycarboxylate chelating parent acids or salts thereof can be supplemented as useful builder components, for example, citric acid or citrate/citric acid mixtures.

Borate builders and builders containing borate-forming materials which are capable of generating borate under detergent storage or wash conditions are water-soluble builders useful herein.

Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate, wherein the degree of polymerization is About 6-21, and phytate.

Partially soluble or insoluble builder compounds

The detergent compositions of the present invention may contain some soluble or insoluble builder compounds, typically at a level of from 0.5% to 60%, preferably from 5% to 50%, most preferably from 8% to 40% by weight of the composition.

Examples of substantially water insoluble builders include sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula _Naz ( _AlO2 ) _z ( _SiO2 ) _y ] _-xH2O , where z and y are at least 6, the molar ratio of z to y is from 1.0 to 0.5, x At least 5, preferably 7.5-276, more preferably 10-264. The aluminosilicate material is in hydrated form, preferably crystalline, containing 10-28%, more preferably 18-22% bound water.

Aluminosilicate zeolites may be natural products, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are commercially available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:

Na ₁₂ [(A1O ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]-xH ₂ O

where x is 20-30, especially 27. Zeolite X has the formula: Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]-276H ₂ O.

Zeolite MAP builder is another preferred aluminosilicate zeolite.

Based on the weight of the composition, the content of zeolite MAP is 1-80%, more preferably 15-40%.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as a zeolite P-type alkali metal aluminosilicate having a silicon to aluminum ratio not greater than 1.33, preferably 0.9-1.33, more preferably 0.9-1.2.

Of particular interest are zeolites MAP having a silicon to aluminum ratio not greater than 1.15, more specifically not greater than 1.07.

In preferred instances, the zeolite MAP detergent builder has a particle size expressed as ad ₅₀ value of 1.0-10.0 μm, more preferably 2.0-7.0 μm, most preferably 2.5-5.0 μm.

The d ₅₀ value means that 50% by weight of the particles have a diameter smaller than this value. Particle size can be determined specifically by conventional analytical techniques, such as microscopic measurement using a scanning electron microscope or measurement with a laser particle size analyzer. Other methods of determining _d50 values are described in EP 384070A.

Heavy metal ion chelating agent

The compositions of the present invention preferably comprise, as an optional ingredient, a heavy metal ion sequestrant. The so-called heavy metal ion chelating agent herein refers to components that play the role of chelating heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferably they exhibit selectivity for binding heavy metal ions such as iron, manganese and copper.

The content of the heavy metal ion chelating agent is generally 0.005-10%, preferably 0.1%-5%, more preferably 0.25-7.5%, most preferably 0.3-2%, of the composition or component weight of the present invention.

Heavy metal ion sequestrants suitable for use in the present invention include organic phosphonates such as aminoalkylene poly(alkylene phosphonates), alkali metal ethane 1-hydroxydiphosphonates and nitrilotrimethylenephosphine salt.

Among the above substances, diethylenetriaminepenta(methylenephosphonate), ethylenediaminetris(methylenephosphonate), hexamethylenediaminetetrakis(methylenephosphonate) and hydroxyl - Ethylene 1,1-diphosphonate, 1,1-hydroxyethanediphosphonic acid and 1,1-hydroxyethane dimethylenephosphonic acid.

Other heavy metal ion sequestrants suitable for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylene Diamine disuccinic acid or any salt thereof.

Other heavy metal ion sequestrants suitable for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid as described in EP-A-317,542 and EP-A-399,133. The present invention can also use iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid as described in EP-A-516,102 Chelating agent. The present invention can also adopt β-alanine-N described in EP-A-509,382, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and Iminodisuccinic acid chelating agent.

EP-A-476,257 discloses suitable amino-based chelating agents. EP-A-510,331 discloses suitable chelating agents derived from collagen, keratin or casein. EP-A-528,859 discloses a suitable alkyliminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Glycineamide-N,N'-disuccinic acid (GADS), Ethylenediamine-N,N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N,N'-disuccinic acid (HPDDS) is also suitable.

Particularly preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N,N'-disuccinic acid (EDDS), 1,1-hydroxyethane diphosphonic acid and 1,1-hydroxyethane dimethylene Phosphonic acids or their alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof.

enzyme

Another preferred ingredient for use in the detergent compositions of the present invention is one or more additional enzymes.

Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, fruit enzymes conventionally added to detergent compositions. Gelase, Lactase and Peroxidase. Suitable enzymes are discussed in US3519570 and US3533139.

Preferred commercially available proteases include those sold under the trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), those sold under the trade names Maxatase, Maxacal and Maxapem by Gist-Brocades Proteases, those sold by Genencor International and those sold under the trade names Opticlean and Optimase by Solvay Enzymes. Proteases may be added to the compositions of the present invention at levels of 0.0001% to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, the alpha-amylases obtained from a specific strain of Bacillus licheniformis as described in detail in GB-1269839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Highly preferred amylases are those described in PCT/US9703635 and WO95/26397 and WO96/23873.

Amylase is added to the composition of the present invention at a level of 0.0001%-2% active enzyme by weight of the composition.

The lipolytic enzyme may be present at an active lipolytic enzyme level of from 0.0001% to 2%, preferably from 0.001% to 1%, most preferably from 0.001% to 0.5%, by weight of the composition.

Lipases may be obtained from fungal or bacterial sources, for example from lipase-producing strains of Humicola, Thermomyces sp. or Pseudomonas, including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipases derived from chemically or genetically modified variants of these strains are also useful in the present invention. A preferred lipase is obtained from Pseudomonas pseudoalcaligenes, which is described in granted European patent EP-B-0218272.

Another preferred lipase of the present invention, as described in European patent application EP-A-0258068, is a lipase obtained by cloning a gene obtained from Humicola lanuginosa and expressing the gene in Aspergillus oryzae as a host, it Commercially available under the tradename Lipolase from Novo Industri A/S Bagsvaerd, Denmark. This lipase is also described in US4810414, Huge-Jensen et al., issued March 7,1989.

organic polymer

Organic polymers are a preferred additional component of the detergent compositions herein, preferably present as a component of any particulate components, where they serve, for example, to bind the particulate components together. By organic polymer is meant herein essentially any organic polymer commonly used as a dispersant, anti-redeposition agent and soil-suspension agent in detergent compositions, including any high molecular weight organic polymer described herein as a clay flocculant. Polymers, including the quaternized ethoxylated (poly)amine soil removers/antiredeposition agents of the present invention.

Organic polymers are typically incorporated in the detergent compositions herein at levels of 0.01-30%, preferably 0.1-15%, more preferably 0.5-10% by weight of the composition.

Examples of organic polymers include water-soluble organic homo- or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 2000-100,000, especially 40,000-80,000.

Polyamino compounds are useful herein and include those derived from aspartic acid, such as those described in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers comprising monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5,000-10,000, are also suitable for use in the present invention.

Other organic polymers suitable for incorporation into the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Other useful organic polymers are polyethylene glycols, especially those having a molecular weight of 1000-10000, more preferably 2000-8000, most preferably about 4000.

Highly preferred polymeric components of the present invention are cotton and non-cotton soil release polymers according to Scheibel et al. US Patent No. 4,968,451 and Gosselink et al.

Another organic compound useful in the present invention, which is a preferred clay dispersant/anti-redeposition agent, can be a cationic ethoxylated monoamine and diamine having the formula:

Wherein X is a nonionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is 0-20, preferably 0-4 (such as ethylene, ethylene propyl, hexamethylene), b is 1 or 0; for cationic monoamines (b=O), n is at least 16, generally in the range of 20-35; for cationic diamines (b=1), n is at least About 12, the general range is about 12 to about 42.

Other dispersants/anti-redeposition agents useful in the present invention are described in EP-B-011965, US4659802 and US4664848.

Antifoam system

When the detergent composition of the present invention is formulated for use in machine wash compositions, a suds suppressor system may be included in an amount of 0.01-15%, preferably 0.02-10%, more preferably 0.05- 3%.

Suitable suds suppressing systems for use in the present invention may comprise essentially any known antifoam compound, including, for example, silicone antifoam compounds and 2-alkyl alkanol antifoam compounds.

By antifoam compound is meant any compound or mixture thereof which acts, for example, to inhibit foaming or sudsing of a detergent composition solution, especially when the solution is agitated.

Particularly preferred antifoam compounds for use in the present invention are silicone antifoam compounds, which are defined herein as any antifoam compound that includes a silicone component. Such silicone antifoam compounds typically also contain a silica component. The term "polysiloxane" as used herein and commonly used in the industry includes various relatively high molecular weight polymers containing siloxane units and various types of hydrocarbyl groups. Preferred silicone antifoam compounds are silicones, especially polydimethylsiloxanes having trimethylsilyl end-capping units.

Other suitable antifoam compounds include monobasic fatty carboxylic acids and soluble salts thereof. These substances are described in US 2954347, issued September 27, 1960 to Wayne St. John. The monohydric fatty carboxylic acids and salts thereof useful as suds suppressors generally have hydrocarbyl chains of 10-24 carbon atoms, preferably 12-18 carbon atoms. Suitable salts include alkali metal salts, such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (such as fatty acid triglycerides), monohydric alcohol fatty acid esters, aliphatic C ₁₈ -C ₄₀ ketones (such as stearyl ketone), N-alkylated amino Triazines, such as tri to hexaalkylmelamines or di to tetraalkyldiamine chlorotriazines, formed as products of cyanuric chloride with 2 or 3 moles of primary or secondary amines containing 1 to 24 carbon atoms propylene oxide, distearic acid amide and monostearyl phosphate dialkali metal (eg sodium, potassium, lithium) salts and phosphate esters.

A preferred suds suppressor system comprises:

(a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising a combination of:

(i) polydimethylsiloxane, its content accounts for 50-99%, preferably 75-95% of polysiloxane defoamer compound; And

(ii) silicon dioxide in an amount of 1-50%, preferably 5-25%, of the polysiloxane/silica defoamer compound;

Wherein the blending amount of the silicon dioxide/polysiloxane antifoaming agent compound is 5%-50%, preferably 10%-40% by weight;

(b) a dispersant compound, most preferably comprising a polysiloxane diol comb copolymer (rakecopolymer) having a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of 1: 0.9-1:1.1 in an amount of 0.5-10%, preferably 1-10% by weight; a particularly preferred polysiloxanediol comb copolymer of this type is DCO544, commercially available under the trade name DCO544 from the company DOW Corning;

(c) an inert carrier fluid compound, most preferably it comprises a C ₁₆ -C ₁₈ ethoxylated alcohol with a degree of ethoxylation of 5-50, preferably 8-15, in an amount of 5-80%, preferably 10-70% by weight.

Highly preferred granular antifoam systems are disclosed in EP-A-0210731 which comprise a polysiloxane antifoam compound and an organic carrier material having a melting point of 50-85°C, wherein the organic carrier material comprises glycerol Monoesters with a fatty acid having a carbon chain of 12-20 carbon atoms. EP-A-0210721 discloses other preferred granular suds suppressor systems in which the organic carrier substance is a fatty acid or alcohol having a carbon chain of 12-20 carbon atoms, or a mixture thereof, with a melting point of 45-80°C.

Other highly preferred suds suppressor systems include polydimethylsiloxane or polysiloxane blends such as polydimethylsiloxane, aluminosilicates and polycarboxylic acid polymers such as copolymers of lactic acid (laic) and acrylic acid thing.

polymeric dye transfer inhibitor

The detergent compositions herein may also comprise from 0.01 to 10%, preferably from 0.05 to 0.5% by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or mixtures thereof, whereby these polymers may be cross-linked polymer.

Fluorescent whitening agent

The detergent compositions herein can also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.

The hydrophilic fluorescent whitening agent that can be used in the present invention has following formula structure:

Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, morpholino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

In the above formula, when R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6- (N-2-Bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid and disodium salt. This particular brightener is commercially available from Ciba-Geigy under the trade designation Tinopal-UNPA-GX. Tinopal-CBS-X and Tinopal-UNPA-GX are preferred hydrophilic optical brighteners for use in the detergent compositions of the present invention.

In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4- Anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid disodium salt. This particular brightener is commercially available from Ciba-Geigy under the tradename Tinopal 5BM-GX.

In the above formula, when _R1 is anilino, _R2 is morpholino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morpholino-s-tri Azin-2-yl)amino]-2,2'-stilbene disulfonic acid sodium salt. Such specific brighteners are commercially available from Ciba-Geigy under the trade names Tinopal-DMS-X and Tinopal AMS-GX.

polymeric soil release agent

Known polymeric soil release agents, hereinafter abbreviated "SRA", may optionally be used in the detergent compositions herein. If used, SRA's generally comprise from 0.01% to 10.0%, typically 0.1% to 5%, preferably 0.2% to 3.0%, by weight of the composition.

Preferred SRA's generally have a hydrophilic portion that hydrophilizes the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic portion that deposits on the hydrophobic fiber and remains attached to it throughout the wash and rinse cycle, thus acting as the hydrophilic portion of fixtures. This can make stains from SRA treatment easier to remove in subsequent washes.

Preferred SRA's include oligomeric terephthalates, which are generally prepared by a process involving at least one transesterification/oligomerization reaction, usually over a metal catalyst such as titanium(IV) alkoxide. The esters can be prepared using other monomers capable of incorporating the ester structure through one, two, three, four or more positions, without, of course, forming a densely cross-linked overall structure.

Suitable SRA's include sulfonation products of substantially linear ester oligomers containing a terephthaloyl oligoester backbone with oxyalkylene oxygen repeat units and allyl derivatives covalently attached to the backbone. Sulfonated terminal moieties are described, for example, in US Patent No. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. The ester oligomer can be prepared by (a) ethoxylating allyl alcohol; (b) combining the product of (a) with dimethyl terephthalate in a two-step transesterification/oligomerization process ("DMT") and 1,2-propanediol ("PG"); and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters in U.S. Patent No. 4,711,730 issued December 8, 1987 to Gosselink et al. Alcohol) methyl ether, DMT, PG and poly(ethylene glycol) (“PEG”) transesterification/oligomerization products. Other examples of SRA's include partially and fully anionically terminated oligoesters such as those derived from ethylene glycol ("EG"), PG, DMT and 3,6- Oligomers of sodium dioxa-8-hydroxyoctane sulfonate; non-ionic end-capped block polyester oligomers in U.S. Patent No. 4,702,857, Gosselink, issued October 27, 1987, such as DMT, methyl Products prepared from (Me)-capped PEG and EG and/or PG, or from mixtures of DMT, EG and/or PG, Me-capped PEG and sodium dimethyl 5-sulfoisophthalate and anions in U.S. Patent No. 4,877,896 issued October 31, 1989 to Maldonado, Gosselink et al., especially sulfoaroyl-terminated terephthalates, which are typically found in both laundry and fabric conditioning products. One example of useful SRA's is an ester composition prepared from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably also containing added PEG, eg, PEG3400.

SRA's also include: simple copolymeric blocks of ethylene or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see May 25, 1976 U.S. Patent No. 3,959,230 of Hays and U.S. Patent No. 3,893,929 of Basadur of Jul. 8, 1975; cellulose derivatives such as hydroxyether cellulose polymers available from Dow by METHOCEL; C ₁ -C ₄ alkyl cellulose and C ₄ hydroxyalkylcelluloses, see US Patent No. 4,000,093, Nicol et al., December 28, 1976; and methyl cellulose ethers having an average degree of substitution (methyl) of about 1.6-2.3 per anhydroglucose unit , The solution viscosity measured at 20° C. is about 80-120 centipoise as a 2% aqueous solution. Such substances are commercially available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methyl cellulose ethers produced by Shin-etsu Kagaku Kogyo KK.

Another class of SRA's includes: (I) nonionic terephthalate esters linked to polyester structures using diisocyanate coupling agents, see U.S. Pat. Nos. 4,201,824 to Violland et al. and U.S. Pat. SRA's having carboxylate end groups prepared by adding trimellitic anhydride to known SRA's to convert the terminal hydroxyl groups to trimellitate esters. With proper choice of catalyst, trimellitic anhydride forms linkages to the terminal groups of the polymer through the isolated carboxylate of trimellitic anhydride rather than by opening the anhydride linkage. Both nonionic and anionic SRA's can be used as starting materials as long as they have hydroxyl end groups that can be esterified, see U.S. Patent 4,525,524 to Tung et al. Other types include: (III) Anionic terephthalate-based SRA's linked to urethanes, see U.S. Patent 4,201,824 to Violland et al.

other optional components

Other optional ingredients suitable for inclusion in the compositions of the present invention include perfumes, pigments and filler salts, with sodium sulfate being the preferred filler salt.

The addition of color specks is highly preferred. The following colored particles are preferred colored particles: Sodium carbonate granules produced by agglomerating and sieving sodium carbonate powder, wherein 75% of the particles have a particle size of 600-850 microns and 25% of the particles have a particle size of 425-600 microns. The granules thus obtained were sprayed with a Monastral Blue BV slurry solution and then dried to obtain speckles containing about 1000 ppm dye.

Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. It is also preferred to incorporate carbonates, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffers, phase regulators, hydrotropes, enzyme stabilizers, polyacids, foam regulators, opacifiers, antioxidants, bactericidal Agents and dyes such as those described in US Patent No. 4,285,841 to Barrat et al., issued August 25, 1981 (which is incorporated herein by reference).

form of composition

The detergent compositions of the present invention can be prepared by various methods including dry blending and agglomerating and/or spray drying of the various compounds contained in the detergent components.

Compositions according to the invention may take a variety of physical forms, including liquid and solid forms such as tablets, cakes, lozenges and bars, preferably granular forms.

The compositions of the present invention may also be used in or in combination with bleach additive compositions, for example those comprising chlorine bleach.

chlorine based bleach

The detergent compositions of the present invention may comprise, as an additional ingredient, chlorine-based bleaching agents. However, since the preferred detergent compositions of the present invention are solids, most liquid chlorine-based bleaches are not suitable for use in these detergent compositions, only granular or powdered chlorine-based bleaches are suitable.

In addition, the detergent compositions of the present invention can be formulated such that they are compatible with chlorine-based bleaches, thereby ensuring that the user can incorporate chlorine-based bleaches into the detergent compositions at the beginning or during the wash cycle.

The chlorine-based bleaches are capable of causing the formation of hypochlorite species in aqueous solutions. The hypochlorite ion is chemically represented by the formula OCT.

Those bleaching agents which produce hypochlorite species in aqueous solutions include alkali and alkaline earth metal hypochlorites, hypochlorite adducts, chloramines, imine chlorides, chloramides and imides. Specific examples of such compounds include sodium hypochlorite, potassium hypochlorite, primary calcium hypochlorite, secondary magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate , sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfonamide, chloramine T, dichloro Amine T, Chloramine B, and Dichloramine B. Preferred bleaching agents for use in the compositions of the present invention are sodium hypochlorite, potassium hypochlorite or mixtures thereof. A preferred chlorine-based bleach may be Triclosan (trade name).

Most of the above hypochlorite-generating bleaches are commercially available in solid or concentrated form which can be dissolved in water during the preparation of the compositions of the present invention. Some of the above materials are commercially available as aqueous solutions.

The components of the granular composition of the invention should preferably have an average particle size such that no more than 25% are particles with a diameter greater than 1.8 mm; no more than 25% are particles with a diameter less than 0.25 mm. Preferably the average particle size is such that 10%-50% of the particles have a diameter of 0.2mm-0.7mm.

The term mean particle size as defined herein is calculated by sieving a sample of the composition over a set of sieves, preferably Tyler sieves, into fractions (usually 5 fractions). The weight fractions thus obtained are plotted against the aperture of the sieve, the average particle size being the aperture size through which 50% by weight of the sample passes.

laundry method

The machine laundry methods of the present invention generally comprise treating soiled garments with an aqueous wash solution comprising dissolved or dispersed in a washing machine an effective amount of the machine laundry detergent composition of the present invention. An effective amount of the detergent composition means dissolving or dispersing 10 g to 300 g of product in a wash solution volume of 5 to 65 liters, which is a typical amount of product and wash solution volume commonly used in conventional machine washing methods.

In a preferred use aspect, the detergent composition is formulated such that it is suitable for hand washing.

In another preferred aspect, the detergent composition is a pretreatment or soaking composition for pretreating or soaking soiled and soiled fabrics.

Abbreviations used in the examples

In detergent compositions, the abbreviated component symbols have the following meanings:

LAS: Sodium linear C _11-13 alkylbenzene sulfonate

TAS : Sodium Tallow Alkyl Sulfate

CxyAS: sodium C _1x -C _1y alkyl sulfate

C46SAS: C ₁₄ -C ₁₆ secondary (2,3) sodium alkyl sulfate

CxyEzS: sodium _C1x - _C1y alkyl sulfate condensed with z moles of ethylene oxide

CxyEz : Condensed with average z moles of ethylene oxide is mainly linear

C _1x -C _1y primary alcohols

QAS: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₁₂ -C ₁₄

QAS1: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₈ -C ₁₁

SADS: C ₁₄ -C ₂₂ alkyl disulfide _of formula 2-(R)C ₄ H ₇ -1,4-(SO ₄ -) 2

Sodium acid, where R = C ₁₀ -C ₁₈

SADE2S: C ₁₄ -C ₂₂ alkyl disulfide _of formula 2-(R)C ₄ H ₇ -1,4-(SO ₄ -) 2

Sodium acid, where R=C ₁₀ -C ₁₈ , condenses z moles of ethylene oxide

MES: x-sulfomethyl esters of _C18 fatty acids

APA: C ₈ -C ₁₀ amidopropyl dimethylamine

Soap: Sodium Linear Alkyl Carboxylate, 80/20 of tallow and coconut fatty acids

The mixture gets

STS : Sodium Toluene Sulfonate

CFAA : C ₁₂ -C ₁₄ (Coco) Alkyl N-Methyl Glucamide

TFAA: C ₁₆ -C ₁₈ Alkyl N-methyl Glucamide

TPKFA: C ₁₆ -C ₁₈ top full fraction fatty acids

STPP : Anhydrous sodium tripolyphosphate

TSPP : Tetrasodium pyrophosphate

Zeolite A: hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .7H ₂ O, initial

The grade particle size is 0.1-10 microns (by weight expressed on anhydrous basis)

NaSKS-6: crystalline layered silicate _{of the} formula δ- _Na2Si2O5

Citric acid: anhydrous citric acid

Borate : sodium borate

Carbonate: anhydrous sodium carbonate with a particle size of 200-900 microns

Bicarbonate: anhydrous sodium bicarbonate with a particle size distribution of 400-1200 microns

Silicate: Amorphous sodium silicate (SiO ₂ :Na ₂ O ratio=2.0:1)

Sulfate : Anhydrous Sodium Sulfate

Magnesium Sulfate: Anhydrous Magnesium Sulfate

Citrate : Trisodium citrate dihydrate, 86.4% active, particle size distribution

At 425-850 microns

MA/AA: 1:4 maleic acid/acrylic acid copolymer, average molecular weight about 70000

MA/AA(1): 4:6 maleic acid/acrylic acid copolymer, average molecular weight about 10000

AA : Sodium polyacrylate polymer with an average molecular weight of 4500

CMC : Sodium Carboxymethyl Cellulose

Cellulose ether: Methyl cellulose ether with a degree of polymerization of 650, by Shin Etsu

Purchased by Chemicals

Protease : sold under the tradename Savinase by Novo Industries A/S

     Proteolytic enzymes for sale with 3.3% active enzyme by weight

Protease I: proteolytic enzyme described in WO95/10591 with 4

% by weight active enzyme, sold by Genencor Int. Inc.

Alcalase: a proteolytic enzyme sold by Novo Industries A/S,

  Has 5.3% by weight active enzyme

Cellulase: marketed by Novo Industries A/S under the trade name Carezyme

      Cellulase enzymes sold with 0.23% by weight active enzyme

Amylase: sold by Novo Industries A/S under the trade name Termamyl

Amylase sold at 120T with 1.6% active enzyme by weight

Amylase II: the amylase disclosed in PCT/US9703635

Lipase: marketed by Novo Industries A/S under the trade name Lipolase

Sold lipolytic enzyme with 2.0% by weight active enzyme

Lipase (1): sold by Novo Industries A/S under the tradename Lipolase

Lipolytic enzyme sold by Ultra with 2.0% active enzyme by weight

Endolase: endoglucanase, sold by Novo Industries A/S,

  Has 1.5% by weight active enzyme

PB4: Sodium perborate tetrahydrate of nominal formula NaBO ₂ .3H ₂ OH ₂ O ₂

PB1 Anhydrous sodium perborate bleach of nominal formula NaBO ₂ .H ₂ O ₂

Percarbonate: Sodium percarbonate of nominal formula 2Na ₂ CO ₃ .3H ₂ O ₂

DOBS Decanoyloxybenzenesulfonate, sodium salt form

DPDA : Diperoxydodecanedioic acid

NOBS : Nonanoyloxybenzenesulfonate, sodium salt form

NACA-OBS : (6-nonanoylaminocaproyl)oxybenzenesulfonate

LOBS : Dodecanoyloxybenzenesulfonate in the sodium salt form

DOBS : Decanoyloxybenzenesulfonate in the sodium salt form

DOBA : Decanoyloxybenzoic Acid

TAED ：Tetraacetylethylenediamine

DTPA : Diethylenetriaminepentaacetic acid

DTPMP: Diethylenetriaminepenta(methylenephosphonic acid), commercialized by Monsanto

Product Name Dequest 2060 Sales

EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer, sodium salt

form

Photoactivated bleaching: sulfonated zinc phthalocyanine encapsulated with a dextrin-soluble polymer

whitening agent (1)

Photoactivated bleaching: sulfonated aluminum phthalocyanine encapsulated with dextrin-soluble polymers

whitening agent (2)

Brightener 1: 4,4'-bis(2-sulfostyrene)biphenyl disodium

Brightener 2: 4,4'-bis(4-anilino-6-morpholino-1,3,5-triazine-2-

Disodium (yl)amino)stilbene-2:2'-disulfonate

HEDP ：Hydroxyethane 1,1-diphosphonic acid

HEDMP ：Hydroxyethane 1,1-dimethylphosphonic acid

PEGx : polyethylene glycol, molecular weight x (generally 4000)

PEO : polyethylene oxide, average molecular weight 50,000

TEPAE : Oxylated tetraethylenepentamine

PVI : Polyvinylimidazole, average molecular weight 20000

PVP : polyvinylpyrrolidone polymer, average molecular weight 60000

PVNO : Polyvinylpyridine N-oxide polymer, average molecular weight

50000

PVPVI : Copolymer of polyvinylpyrrolidone and vinylimidazole, flat

  Average molecular weight 20000

QEA: Di((C ₂ H ₅ O)-(C ₂ H ₄ O) _n )(CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -(CH ₃ )

Di((C ₂ H ₅ O)-(C ₂ H ₄ O)) _n , where n=20-30

SRP1 : Anion-terminated polyester

SRP2 : Ethoxylated poly(1,2-propylene terephthalate) short block

Polymer

PEI : polyethyleneimine, average molecular weight 1800, average ethoxylation

The degree is 7 ethyleneoxy residues per nitrogen atom

Polysiloxane Disinfection: Polydimethylsiloxane Foam Control Agent and Polysiloxane as Dispersant

Foaming agent Alkane-oxyalkylene copolymer, the weight of the foam control agent and the dispersant

The quantity ratio is 10:1-100:1

Sunscreen: Water-based monostyrene latex blend by BASF

Sold under the trade name Lytron 621 by Aktiengesellschaft

Wax : Paraffin

Color Particles : Color Particles as described on page 40 of this article

In the following examples, all contents are expressed in % by weight of the composition:

Example 1

The following detergent formulations are formulations according to the invention: A B C D. blown powder MES 2.0 0.5 1.0 - SADS - - - 2.0 LAS 6.0 5.0 11.0 6.0 TAS 2.0 - - 2.0 Zeolite A 24.0 - - 20.0 STPP - 27.0 24.0 - Sulfate 4.0 6.0 13.0 - MA/AA 1.0 4.0 6.0 2.0

Silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6   Brightener 1 0.2 0.2 0.2 0.2   Polysiloxane defoamer 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 spray on Whitening agent 0.02 - - 0.02 C45E7 - - - 5.0 C45E2 2.5 2.5 2.0 - C45E3 2.6 2.5 2.0 - Spices 0.5 0.3 0.5 0.2   Polysiloxane defoamer 0.3 0.3 0.3 - dry additive QEA - - - 1.0 EDDS 0.3 - - - Sulfates 2.0 3.0 5.0 10.0 carbonate 6.0 13.0 15.0 14.0 Citric acid 2.5 - - 2.0   QASII 0.5 - - 0.5 SKS-6 10.0 - - - Percarbonate 4.0 3.0 - 1.9 PB4 - - 5.0 - NOBS 0.5 - - 0.3 TAED 0.75 0.5 0.2 0.5 DOBS - 0.5 0.6 - Protease 1.0 1.0 1.0 1.0 Lipase - 0.4 - 0.2 Lipase (1) 0.4 - 0.4 - Amylase 0.2 0.2 0.2 0.4   Brightener 1 0.05 - - 0.05 Trace/Minor Components to 100%

Example 2

The following granular detergent formulations are formulations according to the invention: E. f G h I J blown powder LAS 23.0 8.0 7.0 9.0 7.0 7.0 QAS - - - - 1.0 - C45AS 6.0 6.0 5.0 8.0 - - C45AE11S - 1.0 1.0 1.0 - - MES 2.0 - - - 2.0 4.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 MA/AA - 0.5 - - - 2.0 MA/AA(1) 7.0 - - - - - AAA - 3.0 3.0 2.0 3.0 3.0 Sulfate 5.0 6.3 11.1 11.0 11.0 18.1 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 carbonate 15.0 20.0 10.0 20.7 8.0 6.0 PEG4000 0.4 1.5 1.5 1.0 1.0 1.0 DTPA - 0.9 0.5 - - 0.5 Brightener 2 0.3 0.2 0.3 - 0 1 0.3 spray on C45E7 - 2.0 - - 2.0 2.0 C25E9 3.0 - - - - - C23E9 - - 1.5 2.0 - 2.0 spices 0.3 0.3 0.3 2.0 0.3 0.3 Agglomerates C45AS - 5.0 5.0 2.0 - 5.0

LAS - 2.0 2.0 - - 2.0 Zeolite A - 7.5 7.5 8.0 - 7.5 carbonate - 4.0 4.0 5.0 - 4.0 PEG4000 - 0.5 0.5 - - 0.5 Minor components (water, etc.) - 2.0 2.0 2.0 - 2.0 dry additive   QAS(I) - - - - 1.0 - Citric acid - - - - 2.0 - PB4 - 3.0 - - 5 - PB1 - - 4 1.0 - - Percarbonate 2.0 - - 1.0 - 2.0 carbonate - 5.3 1.8 - 4.0 4.0 NOBS 0.5 - 0.4 0.3 - 0.6 DOBS - 0.9 - - 0.3 - TAED 0.6 0.4 0.6 0.3 0.9 0.5 Methylcellulose 0.2 - - - - 0.5 DTPA 0.7 0.5 1.0 0.5 0.5 1.2 SKS-6 8.0 - - - - - STS - - 2.0 - 1.0 - cumenesulfonic acid - 1.0 - - - 2.0 Lipase 0.2 - 0.2 - 0.2 0.4 Cellulase 0.2 0.2 0.2 0.3 0.2 0.2 Amylase II 0.2 - 0.1 - 0.2 - Protease 0.5 0.5 0.5 0.3 0.5 0.5 PVPVI - - - - 0.5 0.1 PVP - - - - 0.5 - PVNO - - 0.5 0.3 - - QEA - - - - 1.0 -

SRP1 0.2 0.5 0.3 - 0.2 -   Polysiloxane defoamer 0.2 0.4 0.2 0.4 0.1 - Magnesium Sulfate - - 0.2 - 0.2 - Spotted ornaments - 2.0 1.0 0.5 2.0 6.0 Trace/minor components to 100%

Example 3

The following granular detergent formulations are formulations according to the invention: K L m N Binder particles STPP - 22.0 - 15.0 Zeolite A 30.0 - 24.0 5.0 Sulfate 5.5 5.0 7.0 7.0 MA/AA 3.0 - - - AAA - 1.6 2.0 - MA/AA(1) - 12.0 - 6.0 LAS 14.0 10.0 9.0 20.0 C45AS 8.0 7.0 9 0 7.0 C45AE11S - 1.0 - 1.0 MES 0.5 4.0 6.0 - SADS 2.5 - - 1.0 Silicate - 1.0 0.5 10.0 soap - 2.0 - - Brightener 1 0.2 0.2 0.2 0 2 carbonate 6.0 9.0 8.0 10.0 PEG4000 - 1.0 1.5 - DTPA - 0.4 - -

spray on C25E9 - - - 5.0 C45E7 1.0 1.0 - - C23E9 - 1.0 2.5 - Spices 0.2 0.3 0.3 - dry additive carbonate 5.0 10.0 13.0 8.0 PVPVI/PVNO 0.5 - 0.3 - Protease 1.0 1.0 1.0 0.5 Lipase 0.4 - - 0.4 Amylase 0.1 - - 0.1 Cellulase 0.1 0.2 0.2 0.1 DTPA/HEDP 0.5 0.3 0.5 1.0 LOBS - 0.8 - 0.3 PB1 5 3.0 10 4.0 DOBA 1.0 - 0.4 - TAED 0.5 0.3 0.5 0.6 Sulfates 4.0 5.0 - 5.0 SRPI - 0.4 - -   Antifoam - 0.5 - - Spotted ornaments 1.0 0.5 - 5.0 Trace/Minor Components to 100%

Example 4

The following compositions are pretreatment compositions according to the invention: o P Q R S T u MES 1.0 2.0 0.8 4.0 - - -

C45E7 6.5 7.5 - - - - - C23E3 - 2.0 5.0 5.0 7.0 9.0 3.0 C25E2.5S 10.0 14.0 17.0 8.0 5.0 15.0 20.0 SADS - - 3.0 - 1.0 1.0 2.0 Acetyl triethyl citrate 3.5 4.0 2.5 - - 3.0 3.5 Percarbonate - - 3.0 2.0 3.0 - - Perborate 2.0 3.0 - - - 1.0 5.0 NACA-OBS - 0.3 - - - 0.6 0.4 NOBS/LOBS/DOBS 1.0 - 1.0 0.2 0.4 - - TAED 0.5 0.6 0.3 0.8 0.9 0.4 0.7 Chelating agent 0.3 0.5 - - 0.2 - 0.8 Water and minor components _{H2SO4 up} to pH4

Example 5

V W X Y Z AA BB Sodium C ₁₁ -C ₁₃ Alkylbenzene Sulfonate 12.0 16.0 23.0 19 18.0 20.0 16.0 Sodium C ₁₄ -C ₁₅ Alcohol Sulfate 4.5 - - - 4.0 C ₁₄ -C ₁₅ Alcohol Ethoxylate (0.5) Sulfate - - - - - C ₁₄ -C ₁₅ Alcohol Ethoxylates (3) Sulfates - - 2.0 - 1.0 1.0 1.0 Sodium C ₁₄ -C ₁₅ Alcohol Ethoxylate (3.0) 2.0 2.0 - 1.3 - - 0.6 C ₉ -C ₁₄ alkyl dimethyl hydroxyethyl quaternary ammonium salt - - 1.0 0.5 2.0 tallow fatty acid - - - - 1.0 Tallow Alcohol Ethoxylate (50) - - - - - - - sodium tripolyphosphate 23.0 25.0 24.0 22.0 20.0 15.0 20.0 Sodium carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0 Sodium polyacrylate (45%) 0.5 0.5 0.5 0.5 - - - Sodium Polyacrylate/Sodium Maleate Polymer - - 1.0 1.0 1.0 2.0 0.5 Sodium silicate (NaO/ _SiO2 ratio 1:6) (46%) 3.0 6.0 9.0 8.0 9.0 6.0 8.0 sodium sulfate 25.0 18.0 20.0 18.0 20.0 22.0 13.0 sodium perborate 5.0 5.0 10.0 8.0 3.0 1.0 2.0 Poly (ethylene glycol), MW ~ 4000 (50%) 1.5 1.5 1.0 1.0 - - 0.5 Sodium carboxymethyl cellulose 1.0 1.0 1.0 - 0.5 0.5 0.5

citric acid - - - - - - - NOBS/DOBS 0.5 1.0 0.5 0.5 1.0 0.7 0.3 TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5 Soil Release Agent Polymer ¹ 1.5 1.5 1.0 1.0 - 1.0 - Soil release agent polymer ² - - - - 1.0 - 1.0 moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0 magnesium sulfate - - - - 1.0 0.5 1.5 Spotted ornaments 0.5 3.0 - 5.0 2.0 - 0.2 Chelating agent - - - - 0.8 0.6 1.0 Enzymes, including amylase, amylase II, cellulase, protease, and lipase - - - - 2.0 1.5 2.0 Minor components such as fragrances, brighteners, photobleaches, dyes 1.0 1.0 1.0 1.0 0.5 1.5 1.0

1. Non-cotton fabric soil release agent polymers according to US Patent No. 5,415,807, issued May 16, 1995 to Gosselink, Pan, Kellett and Hall.

2. Non-cotton fabric soil release polymers according to US Patent Application No. 60/051517.

Example 6

CC DD EE FF Sodium C ₁₁ -C ₁₃ Alkylbenzene Sulfonate 13.3 13.7 10.4 8.0 Sodium C ₁₄ -C ₁₅ Alcohol Sulfate 3.9 4.0 4.5 - C ₁₄ -C ₁₅ Alcohol Ethoxylate (0.5) Sulfate 2.0 2.0 - - C ₁₄ -C ₁₅ Alcohol Ethoxylates (3) Sulfates - - - - Sodium C ₁₄ -C ₁₅ Alcohol Ethoxylate (6.5) 0.5 0.5 0.5 5.0

C ₉ -C ₁₄ alkyl dimethyl hydroxyethyl quaternary ammonium salt 1.0 - - 0.5 tallow fatty acid 0.5 - - - Tallow Alcohol Ethoxylate (50) - - 1.0 0.3 sodium tripolyphosphate - 41.0 - 20.0 Zeolite A, hydrate (0.1-10 microns) 26.3 - 21.3 1.0 Sodium carbonate 23.9 12.4 25.2 17.0 Sodium polyacrylate (45%) 3.4 0.0 2.7 - Sodium Polyacrylate/Sodium Maleate Polymer - - 1.0 1.5 Sodium silicate (NaO/ _SiO2 ratio 1:6) (46%) 2.4 6.4 2.1 6.0 sodium sulfate 10.5 10.9 8.2 15.0 sodium perborate 1.0 1.0 1.0 2.0 Poly (ethylene glycol), MW ~ 4000 (50%) 1.7 0.4 1.0 - Sodium carboxymethyl cellulose 1.0 - - 0.3 citric acid - - 3.0 - NOBS/DOBS 0.2 0.5 0.5 0.1 TAED 0.6 0.5 0.4 0.3 Soil Release Agent Polymer ¹ 1.5 - - - Soil release agent polymer ² - 1.5 1.0 1.0 moisture 7.5 3.1 6.1 7.3 magnesium sulfate - - - 1.0 Chelating agent - - - 0.5

Enzymes, including amylase, amylase II, cellulase, protease, and lipase - 1.0 - 1.5 Minor components such as fragrances, brighteners, photobleaches, dyes 1.0 1.0 1.0 1.0

1. Non-cotton fabric soil release agent polymers according to US Patent No. 4,968,451, Scheibel et al., issued November 6,1990.

2. Non-cotton fabric soil release polymers according to US Patent Application No. 60/051517.

Claims (10)

1. A detergent composition having a density of 330 g/l to 700 g/l comprising a hydrophilic peracid bleach or precursor thereof, a hydrophobic peracid bleach or precursor thereof, and a peroxide source A bleaching system characterized in that the total amount of available oxygen (AvO-a) obtained from the hydrophilic peracid bleach and the hydrophobic peracid bleach is less than 5000 ppm by weight of the composition, and the effective amount of the hydrophobic peracid or precursor The ratio of oxygen (AvO-hb) to available oxygen (AvO-hp) of the hydrophilic peracid or precursor is 3:1-1:50, and the ratio of available oxygen (AvO-o) of the peroxide source to AvO-a The ratio is at least 2:1. 2. A detergent composition according to claim 1, wherein the hydrophilic bleach precursor comprises tetraacetylethylenediamine. 3. A detergent composition according to claim 2, wherein the hydrophobic peracid or precursor comprises a hydrophobic base derived from a fatty acid containing at least 8 carbon atoms. 4. A detergent composition according to claim 3, wherein the hydrophobic peracid or precursor has a dobesylate leaving group. 5. A detergent composition according to any preceding claim wherein the ratio of AvO-o to AvO-a is at least 3:1. 6. A detergent composition according to claim 5, wherein the ratio of AvO-o to AvO-a is at least 4:1. 7. A detergent composition according to claim 1 or 2 comprising a phosphate builder. 8. A detergent composition according to claim 1 wherein the peroxide source bleach comprises one or more inorganic perhydrate salts. 9. A detergent composition according to claim 8, wherein the peroxide source bleach comprises one or more perborates or percarbonates. 10. A detergent composition according to claim 1 comprising one or more enzymes.